Explosive monomers and polymers



United States Patent 3,025,318 EXPLOSIVE MONOMERS AND POLYMERS Robert W. Van Dolah, Pittsburgh, Pa., and Irving B.

.lofie, Buffalo, N.Y., assignors to the United States of America as represented by the Secretary of the Navy N0 Drawing. Filed Oct. 31, 1955, Ser. No. 544,096

11 Claims. (Cl. 260--486) (Granted under Title 35, US. Code (1952), see. 266) The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This invention relates to compounds having the type formula wherein R is hydrogen, alkenoxy or acryloxy, R is alkenoxy or acryloxy and x is an integer.

The compounds are prepared by the reaction of unsaturated alcohols, acids and salts with linear nitramines of the type formula wherein R and R are nitroxy and x is an integer. The compounds have utility as intermediates in the preparation of polymers and co-polymers which are useful as explosives.

Compounds illustrative of the invention are prepared in accordance with the following examples.

Example 1 0.0027 mole of ATX (1,7-dinitroxy-2,4,6-trinitro-2,4,6- triaza heptane) was mixed with 0.0085 mole of sodium acrylate, cc. of glacial acrylic acid and 1 gram of hydroquinone. The mixture was heated with stirring at 100 C. for 20 minutes and poured into 200 cc. of water containing ice. The slurry was filtered, washed with water, methanol and ether and then recrystallized twice from acetic acid. The compound is a white solid having a melting point of 149-149.2 C. Analysis of the compound gave the following results:

Calculated Found The compound has the following structural formula: w i e? 1? 1? ii IL-C: -C-O-C-N--(J-N-C- --"3o--C--o=o-H H H H H (1,7fdiacryloxy-2,4,6-trinitro-2,4,6-triaza heptane) The polymerization of the above compound is illustrated by the following example: .583 g. of the above compound and .0174 g. of benzoyl peroxide were re fiuxed with 10 cc. of methyl acetate for 1 hour and the polymerization product filtered out and dried. The yield of polymer was .52 gram. The product was extremely insoluble in ordinary solvents.

Example 11 2 g. of NSX (1-nitroxy-2,4,6-trinitro-2,4,6-triaza heptane), 1.4 g. sodium acrylate, 15 cc. of acrylic acid and 1 g. of hydroquinone were heated with slurry at 90 C. for 10 minutes and poured into 350 cc. of water containing then filtered and washed with both The compound formed is a white ice. The mixture was methanol and ether.

"ice

solid having a melting point of 143.5" C. lowing structural formula:

5 1? 1? i a H--CN-o-N-(\3N--(J--o--CG=C-H I i H H H (1-acryloxy-2,4,6-trinitro2,4,6-triaza hcptane) (ATTH) Polymerization of the above compound is illustrated by the following examples: .661 g. of the compound, .0132 g. of benzoyl peroxide and 15 cc. of methyl acetate were refluxed at 60 C. for 18 hours and the polymerization product filtered out and dried. A yield of .6 g. of polymer was obtained. The product had a softening point of 143 C., and .19 g. in 3.2 cc. of dimethyl formamide gave a viscosity of 16.28 poises at 23 C. It was found to have a heat of explosion of 705 cal./g., a specific impulse of 210220 lb. sec./ lb. (calculated), and a It has the folmolecular weight of 52,000 (osmometric method). The

polymer product gave the following analysis:

Calculated Found g. of vinyl acetate, 10 cc. of of benzoyl peroxide were re- .4 g. of the compound, .116 methyl acetate and .016 g. fiuxed 18 hours, the product filtered out and washed with A 35 percent yield of polymer was obtained. The polymer had a melting point of 135 C. Analysis of the polymer for nitrogen gave 20.79 percent calculated and 19.8 percent found. The compound was also copolymerized with methyl methacrylate and vinyl chloride.

methyl acetate.

Example 111 3 g. of NSX in Copolymerization of the above compound is illustrated by the following example: .576 g. of the above compound, .115 g. of ATTH, .021 g. of benzoyl peroxide, and 15 cc. of methyl acetate were refluxed for 18 hours, the mixture poured into methanol and filtered. A yield of .20 g. of copolymer having a melting point of 93-120 C. was obtained. .4 g. of allyl ether was recovered in the process indicating that the copolymer ratio was 1 to 1.

Example IV 4 g. of ATX in 25 cc. of allyl alcohol was heated at C. under nitrogen. The mixture was cooled to room temperature and filtered. The compound formed was a white solid having a melting point of 47.5 C. Analysis of the compound gave the following results:

Calculated Found The compound has the following structural formula:

(1,7-dially1oxy-2,4,6-tr1nitro-2,4,6-triazu heptane) Copolymerization of the compound is illustrated by the following example: .803 g. of the compound, .354 g. of ATTH and .034 g. of benzoyl peroxide were heated at 80 C. for 24 hours, mixed with methanol, filtered and the product dried. The copolymer had a softening point of 110 C. It is insoluble in ordinary solvents and can be molded at 100 C. and 800 lbs. pressure.

As illustrated by the above data, all of the compounds of the invention form polymers and copolymers which can be utilized as explosives and propellants.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described.

What is claimed is:

1. Compounds of the formula IITO: R CH2 (-N-CHz) 1R2 wherein R is a member of the group consisting of hydrogen, acryloxy and lower alkenoxy; R is a member of the group consisting of acryloxy and lower alkenoxy; and x is 3.

3. The ester of the formula N02 HoHz(1 IOH)30 OH=CHQ 4. The ester of the formula N 02 oHz=oHgOCH2)'1 TOH2)3 CH=OHz 5. The ether of the formula N 02 HCH2(1 ICH2)aO CH2CH=CH2 6. The ether of the formula N O 2 OHz=CHCHzOCHz(NGHz) OCH;CH=CHz 7. A polymer of the ester having in its monomeric form the formula:

8. A copolymer formed by refluxing for 18 hours a mixture of .4 gram of 1-acryloxy-2,4,6-trinitro-2,4,6-triaza heptane, .116 gram of vinyl acetate, 10 cc. of methyl acetate and .016 gram of benzoyl peroxide.

9. A polymer of the ester having in its monomeric form the formula:

10. A copolymer formed by refluxing for 18 hours at C. a mixture of .576 gram of 1-allyloxy-2,4,6-trinitro- 2,4,6-triaza heptane, .115 gram of 1-acryloxy-2,4,6-trinitro-2,4,6-triaza heptane, .0132 gram of benzoyl peroxide and 15 cc. of methyl acetate.

11. A copolymer formed by heating at C. for 24 hours .803 gram of 1,7-diallyloxy-2,4,6-trinitro-2,4,6-tri aza heptane, .354 gram of l-acryloxy-2,4,6-trinitro-2,4,6- triaza heptane and .034 gram of benzoyl peroxide.

References Cited in the file of this patent FOREIGN PATENTS 615,793 Great Britain Ian. 11, 1949 

1. COMPOUNDS OF THE FORMULA
 7. A POLYMER OF THE ESTER HAVING IN ITS MONOMERIC FORM THE FORMULA: 